CN114487020A - Gas-sensitive material for lung cancer breath marker gas methanol and preparation method thereof - Google Patents
Gas-sensitive material for lung cancer breath marker gas methanol and preparation method thereof Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 239000000463 material Substances 0.000 title claims abstract description 83
- 206010058467 Lung neoplasm malignant Diseases 0.000 title claims abstract description 30
- 201000005202 lung cancer Diseases 0.000 title claims abstract description 30
- 208000020816 lung neoplasm Diseases 0.000 title claims abstract description 30
- 239000003550 marker Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002073 nanorod Substances 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims description 32
- 238000000576 coating method Methods 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 30
- 239000011248 coating agent Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- 230000000241 respiratory effect Effects 0.000 claims description 20
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 238000007789 sealing Methods 0.000 claims description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 239000010935 stainless steel Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 5
- 239000002086 nanomaterial Substances 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 117
- 239000002105 nanoparticle Substances 0.000 description 48
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 45
- 238000012360 testing method Methods 0.000 description 12
- 238000001514 detection method Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 4
- 206010028980 Neoplasm Diseases 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 201000011510 cancer Diseases 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 208000000860 Compassion Fatigue Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000013399 early diagnosis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-Butanol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention discloses a gas-sensitive material for lung cancer breath marker gas methanol and a preparation method thereof, wherein the gas-sensitive material consists of a plurality of crossed nano rods, the diameter of each nano rod is 0.2-0.3 mu m, the length of each nano rod is 10-20 mu m, and the gas-sensitive material can be used for detecting the concentration of methanol, and is particularly suitable for being used as a preferable new material for detecting the lung cancer early breath marker gas methanol.
Description
Technical Field
The invention belongs to the field of material processing, and particularly relates to a gas-sensitive material for lung cancer breath marker gas methanol and a preparation method thereof.
Background
Lung cancer, a cancer with a very high mortality rate, requires early diagnosis. Among them, the laboratory analysis method is the key to accurate and early tumor discovery due to its effectiveness. However, the prior art has the defects that the biomarker potential with long time consumption and high cost is not fully developed, and the conventional diagnostic technology can cause secondary trauma to the human body. There is a need to develop a new method for lung cancer detection with high sensitivity and rapidity. Noninvasive early detection can be performed by analyzing the respiratory gas composition. Methanol as lungOne of the cancer respiratory gas marker gases can be used as a detection gas. According to medical reports and literature, lung cancer patients exhale lower methanol gas than normal people, so that detection of low-concentration methanol gas is helpful for diagnosis of lung cancer. Methanol is a volatile organic compound, is a saturated monohydric alcohol with the simplest structure, has a molecular weight of 32.04, a boiling point of 64.7 deg.C, and a chemical formula of CH3And (5) OH. Has certain toxicity, contains 4% of methanol in industrial alcohol in nervous system and blood system of human body, and the fatal amount is 70 ml.
Metal Oxide Semiconductors (MOS) are receiving much attention due to their excellent gas sensing properties. Compared with the common material, the micro-nano material has better gas sensing performance and adsorption characteristic mainly due to the size, shape and structure of the micro-nano material. In the sensing material of MOS material, it has spinel structure (AB)2O4) Cobaltosic oxide (Co)3O4Particularly prominent with iron oxide (Fe)3O4) All belong to heteroisomorphs having (Co)2+/Co3+) Is a P-type semiconductor material. Cobaltosic oxide (Co)3O4) Can be regarded as Co2O3The combination of CoO and CoO has stable property at 800 deg.C, and is insoluble in water and various acids at normal temperature, so that it can be used for preparing gas-sensitive sensor with good stability and moisture resistance. Co3O4The preparation method mainly comprises a thermal decomposition method, a chemical vapor deposition method, a spray thermal decomposition method, a hydrothermal method, a sol-gel method, a template method and the like, and the Co aiming at the methanol is adopted at present3O4The gas sensor is mainly applied to the detection of the concentration of methanol gas in the air, and is rarely used for the detection under low concentration.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made keeping in mind the above and/or other problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a gas-sensitive material for lung cancer respiratory marker gas methanol and a preparation method thereof.
In order to solve the technical problems, the invention provides the following technical scheme: a gas-sensitive material for lung cancer breath marker gas methanol comprises,
the nano-scale structure comprises a plurality of groups of nano-components which are crossed together, wherein each nano-component comprises a plurality of nano-rods which are stacked together or are closely connected together, the diameter of each nano-rod is 0.2-0.3 mu m, and the length of each nano-rod is 10-20 mu m.
The invention aims to overcome the defects in the prior art and provide the application of a gas-sensitive material for lung cancer breath marker gas methanol in preparing a gas-sensitive element for detecting low-concentration methanol.
The method for preparing the gas sensitive material for the lung cancer respiratory marker gas methanol comprises the following steps,
dissolving cobalt salt, urea and ammonium fluoride in deionized water, and magnetically stirring at room temperature to obtain a mixed solution;
transferring the mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, heating for reaction for a period of time, naturally cooling to room temperature after the reaction is finished, centrifuging, washing and drying to obtain a precursor material;
and (3) carrying out heat treatment on the precursor material in air, and then naturally cooling to room temperature to obtain the gas-sensitive material.
As a preferred embodiment of the method for preparing a gas sensitive material for lung cancer respiratory marker gas methanol according to the present invention, wherein: the cobalt salt includes but is not limited to Co (NO)3)2·6H2O。
As a preferred embodiment of the method for preparing a gas sensitive material for lung cancer respiratory marker gas methanol according to the present invention, wherein: the mixed solution contains 4.05g of Co (NO) per 40ml of the mixed solution3)2·6H2O、4.05g～4.5g of CO (NH)2)2And 0.056g to 0.06g of NH4F, the balance being deionized water
As a preferred embodiment of the method for preparing a gas sensitive material for lung cancer respiratory marker gas methanol according to the present invention, wherein: the mixed solution contains 4.05g of Co (NO) per 40ml of the mixed solution3)2·6H2O, 4.05g of CO (NH)2)20.056g of NH4F, and the balance of deionized water.
As a preferred embodiment of the method for preparing a gas sensitive material for lung cancer respiratory marker gas methanol according to the present invention, wherein: the reaction temperature is 130 ℃, and the reaction time is 9 h.
As a preferred embodiment of the method for preparing a gas sensitive material for lung cancer respiratory marker gas methanol according to the present invention, wherein: the temperature of the heat treatment was 350 ℃.
As a preferable scheme of the application of the product prepared by the invention, the method comprises the following steps: adding a gas-sensitive material into deionized water, grinding to form paste, uniformly coating the paste on the surface of a gas sensor, completely covering a platinum electrode, and drying at room temperature for 12 hours to form a gas-sensitive coating;
and (3) preheating the gas sensor with the dried coating in air at 300 ℃ for 24 hours.
The invention has the beneficial effects that:
(1) the gas-sensitive material structure has the advantages of large specific surface area, high electron mobility, simple and safe preparation method, low cost and high practicability, and fills up the defect of detecting CH under the condition of low concentration3Blank OH gas response.
(2) The gas-sensitive material prepared by the invention has the sensitivity of 19 to 5ppm of methanol gas at the optimal working temperature of 200 ℃ under the conditions of lower working temperature and relative humidity of 0-80%, has specific sensing characteristics to the methanol gas, and can realize effective detection of the methanol at low temperature.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 shows the reaction time of 9h of hydrothermal reaction3O4SEM morphology of nanoparticles (5 μm/10 μm).
FIG. 2 shows the reaction time of 9h for hydrothermal reaction3O4Nanoparticle SEM topography (500 nm).
FIG. 3 shows the reaction time of 9h for hydrothermal reaction3O4Nanoparticle XRD pattern.
FIG. 4 shows the reaction time of 9h hydrothermal reaction of Co3O4Dynamic response curve of nanoparticles to low concentration of methanol at 50% relative humidity.
FIG. 5 shows a spherical shape of Co3O4SEM topography (1 μm) of the nanoparticle cluster material.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The gas-sensitive material for lung cancer respiratory marker gas methanol has a micro-morphology structure (as shown in figures 1 and 2) which is composed of a plurality of groups of nano components, wherein the nano components are crossed together to form a bow tie, the nano components are composed of a plurality of nanorods stacked together or closely attached together, the diameter of each nanorod is 0.2-0.3 mu m, and the length of each nanorod is 10-20 mu m.
The gas-sensitive material has the advantages of large specific surface area, high electron mobility, simple and safe preparation method, low cost and high practicability, and fills up the defect of detecting CH under the condition of low concentration3Blank OH gas response.
The method for preparing the gas sensitive material for the lung cancer respiratory marker gas methanol comprises the following steps,
dissolving cobalt salt, urea and ammonium fluoride in deionized water, and magnetically stirring at room temperature to obtain a mixed solution, wherein each 40ml of the mixed solution contains 4.05g of Co (NO)3)2·6H2O, 4.05g of CO (NH)2)20.056g of NH4F, the balance being deionized water;
transferring the mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, reacting at 130 ℃ for 9 hours, naturally cooling to room temperature after the reaction is finished, centrifuging, washing and drying to obtain a precursor material;
and (3) carrying out heat treatment on the precursor material in air, and then naturally cooling to room temperature to obtain the gas-sensitive material.
Example 1
(1) At normal temperature, 4.05g of Co (NO) is added3)26H2O, 4.05g of CO (NH)2)20.056g of NH4F, mixing with a proper amount of deionized water, and magnetically stirring to obtain 40ml of uniform mixed solution;
(2) transferring the obtained mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, reacting for 9 hours at 130 ℃, naturally cooling to room temperature after the reaction is finished, centrifuging, washing, and drying the product for 2 hours at 110 ℃ to obtain a precursor material;
(3) carrying out heat treatment on the obtained material precursor in air, wherein the heat treatment temperature is 350 ℃, keeping the temperature for 2h, the heating rate is 5 ℃/min, and then naturally cooling to room temperature to obtain Co3O4Tie-knot type nanoparticle cluster materialPreparing materials;
(4) adding deionized water into the obtained material, grinding to form paste, then uniformly coating the paste on the surface of the gas sensor, completely covering the platinum electrode, and drying at room temperature for 12h to form the gas-sensitive coating. Preheating the gas sensor with the dry coating in air at 300 ℃ for 24 hours to obtain Co3O4A bow-tie nanoparticle gas sensor.
To Co3O4SEM and XRD detection is carried out on the bow-tie type nanoparticle gas sensor, and the appearance of the bow-tie type nanoparticle and Co are found3O4The phase, the specific surface area of the contact gas can be increased by the morphological structure, higher response is obtained during testing, and the response can be enhanced by comparing different preparation conditions and adding doping elements.
Example 2
(1) Co based on preparation of example 13O4On a bow tie type nanoparticle gas sensor, 4.22g of CoSO47H2O, 4.50g of CO (NH)2)21.11g of NH4F, mixing with a proper amount of deionized water, and magnetically stirring to obtain 40ml of uniform mixed solution;
(2) transferring the obtained mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, reacting for 12 hours at 100 ℃, naturally cooling to room temperature after the reaction is finished, centrifuging, washing, and drying the product for 6 hours at 80 ℃ to obtain a precursor material;
(3) carrying out heat treatment on the obtained material precursor in air at the heat treatment temperature of 300 ℃, keeping the temperature for 3h, wherein the heating rate is 1 ℃/min, and then naturally cooling to room temperature to obtain Co3O4Spherical nanoparticle cluster materials;
(4) adding deionized water into the obtained material, grinding to form paste, then uniformly coating the paste on the surface of the gas sensor, completely covering the platinum electrode, and drying at room temperature for 12h to form the gas-sensitive coating. Preheating the gas sensor with the dry coating in air at 300 ℃ for 24 hours to obtain Co3O4Spherical nanoparticle gas sensors, e.g.As shown in fig. 5.
The flow meter is adjusted to feed in CH with the concentration of 5ppm3OH, comparative Co3O4Bow tie type nanoparticle gas sensor and Co3O4Response of spherical nanoparticle gas sensors.
At 5ppm methanol, Co3O4Bow tie type nanoparticle gas sensor and Co3O4The response of the spherical nanoparticle gas sensor is 19.1 and 5.1 respectively. From the experimental data, Co3O4The collar type nanoparticle gas sensor has the best response value, and the response value is 5ppm of CH3The OH response value can reach 19.1.
Example 3
(1) Co based on preparation of example 13O4On a knot type nanoparticle gas sensor, 4.05g of Co (NO) is added at normal temperature3)2·6H2O, 4.05g of CO (NH)2)20.056g of NH4F, mixing with a proper amount of deionized water, and magnetically stirring to obtain 40ml of uniform mixed solution;
(2) three portions of the same mixed solution were prepared, and 0.062g, 0.186g, and 0.310g of Eu (NO) were added3)3·6H2O, doping as a dopant;
(3) transferring the obtained mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, reacting for 9 hours at 130 ℃, naturally cooling to room temperature after the reaction is finished, centrifuging, washing, and drying the product for 2 hours at 110 ℃ to obtain a precursor material;
(4) carrying out heat treatment on the obtained material precursor in the air, wherein the heat treatment temperature is 350 ℃, keeping the temperature for 2h, the heating rate is 5 ℃/min, and then naturally cooling to room temperature to obtain Eu-Co3O4A bow-tie nanoparticle cluster material;
(5) adding deionized water into the obtained material, grinding to form paste, then uniformly coating the paste on the surface of the gas sensor, completely covering the platinum electrode, and drying at room temperature for 12h to form the gas-sensitive coating. Preheating the gas sensor with the dry coating in air, and keeping the temperatureThe temperature is 300 ℃ and the time is 24 hours to obtain Eu-Co3O4A bow-tie nanoparticle gas sensor;
the flow meter is adjusted to feed in CH with the concentration of 5ppm3OH, comparative Co3O4Tie-knot type nanoparticle gas sensor and Eu-Co with different doping ratios3O4Response of bow-tie nanoparticle gas sensors.
Co at 5ppm methanol concentration3O4Tie-knot type nanoparticle gas sensor and Eu-Co with different doping ratios3O4When the bow-tie type nanoparticle gas sensor responds, Co3O4Has a response value of 19.1, 1wt% Eu-Co3O4Has a response value of 7.5, 3wt% Eu-Co3O4Has a response value of 12.1, 5wt% Eu-Co3O4The response value of (a) was 4.5. From the data, comparative Co3O4Tie-knot type nanoparticle gas sensor and Eu-Co with different doping ratios3O4The response of the bow-tie nanoparticle gas sensor can be observed, Co3O4Shows better pair CH3OH response, doping Eu aimed at reducing the redox reaction capability, but by comparison it can be seen that pure Co3O4The bow-tie type nano-particle material is more than the Eu-Co after doping3O4To CH3The OH response is better.
Example 4
(1) At normal temperature, 4.05g of Co (NO) is added3)2·6H2O, 4.05g of CO (NH)2)20.056g of NH4F, mixing with a proper amount of deionized water, and magnetically stirring to obtain 40ml of uniform mixed solution;
(2) transferring the obtained mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, reacting for 9 hours at 130 ℃, naturally cooling to room temperature after the reaction is finished, centrifuging, washing, and drying the product for 2 hours at 110 ℃ to obtain a precursor material;
(3) carrying out heat treatment on the obtained material precursor in air, wherein the heat treatment temperature is 350 ℃, keeping the temperature for 2h, the heating rate is 5 ℃/min, then naturally cooling to room temperature,to obtain Co3O4A bow-tie nanoparticle cluster material;
(4) adding deionized water into the obtained material, grinding to form paste, then uniformly coating the paste on the surface of the gas sensor, completely covering the platinum electrode, and drying at room temperature for 12h to form the gas-sensitive coating. Preheating the gas sensor with the dry coating in air at 300 ℃ for 24 hours to obtain Co3O4A bow-tie nanoparticle gas sensor.
Methanol CH with the concentration of 5ppm is respectively introduced by adjusting a flowmeter3OH, ethanol C2H5OH, n-butanol CH3(CH2)3OH, comparative Co3O4The selectivity of the bow-tie type nano-particle gas to different alcohol gases with the same concentration.
In Co3O4Response of the neckline type nanoparticle gas sensor to different alcohol gases at a concentration of 5ppm for CH3OH response value of 19.1 to C2H5OH response value of 4.65 to CH3(CH2)3The OH response value was 5. From the data, it can be concluded that Co is present in different alcohol gases at a concentration of 5ppm3O4Bow tie type nano particle to methanol CH3OH response is highest, and the smaller molecular weight of methanol for Co3O4The adsorption of the nano-particles in the shape of the bow knot is easier to cause, and proves that the nano-particles have better selectivity for alcohol gases.
Example 5
(1) At normal temperature, 4.05g of Co (NO) is added3)2·6H2O, 4.05g of CO (NH)2)20.056g of NH4F, mixing with a proper amount of deionized water, and magnetically stirring to obtain 40ml of uniform mixed solution;
(2) transferring the obtained mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, reacting for 9 hours at 130 ℃, naturally cooling to room temperature after the reaction is finished, centrifuging, washing, and drying the product for 2 hours at 110 ℃ to obtain a precursor material;
(3) the precursor of the obtained material is in the airPerforming heat treatment at 350 deg.C for 2h with a heating rate of 5 deg.C/min, and naturally cooling to room temperature to obtain Co3O4A bow-tie nanoparticle cluster material;
(4) adding deionized water into the obtained material, grinding to form paste, then uniformly coating the paste on the surface of the gas sensor, completely covering the platinum electrode, and drying at room temperature for 12h to form the gas-sensitive coating. Preheating the gas sensor with the dry coating in air at 300 ℃ for 24 hours to obtain Co3O4A bow-tie nanoparticle gas sensor;
(5) the flow meter is adjusted to feed in CH with the concentration of 5ppm3OH, test Co3O4Stability of the ligated nanoparticle gas sensor within one month.
The response value is maintained between 18.5 and 19.1 in one month, and the low concentration CH is generated3And under the OH detection condition, the response value is better.
Example 6
(1) At normal temperature, 4.05g of Co (NO) is added3)2·6H2O, 4.05g of CO (NH)2)20.056g of NH4F, mixing with a proper amount of deionized water, and magnetically stirring to obtain 40ml of uniform mixed solution;
(2) transferring the obtained mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, reacting for 9 hours at 130 ℃, naturally cooling to room temperature after the reaction is finished, centrifuging, washing, and drying the product for 2 hours at 110 ℃ to obtain a precursor material;
(3) carrying out heat treatment on the obtained material precursor in air, wherein the heat treatment temperature is 350 ℃, keeping the temperature for 2h, the heating rate is 5 ℃/min, and then naturally cooling to room temperature to obtain Co3O4A bow-tie nanoparticle cluster material;
(4) adding deionized water into the obtained material, grinding to form paste, then uniformly coating the paste on the surface of the gas sensor, completely covering the platinum electrode, and drying at room temperature for 12h to form the gas-sensitive coating. Gas sensors with dry coatings in the airPreheating in air at 300 deg.C for 24 hr to obtain Co3O4A bow-tie nanoparticle gas sensor;
(5) the flow meter is adjusted to feed in 0.5ppm, 1ppm and 5ppm of CH3OH, test Co3O4The collar-type nanoparticle gas sensor has a response value to a lower concentration.
In addition, the concentration of CH at 100 ℃, 150 ℃, 200 ℃ and 250 ℃ of 5ppm was measured by controlling the temperature3Response value to OH, test Co3O4The optimal corresponding temperature of the bow-tie nanoparticle gas sensor is that the response value is 9.6 at 100 ℃, the response value is 19.1 at 200 ℃ and the response value is 10.3 at 250 ℃, the response values are 7.23 and 150 ℃; at 200 ℃, the gas-sensitive material has a CH concentration of 5ppm3Best response value of OH.
The response value for 0.5ppm is about 2, the response value for 1ppm is about 3.5, and the response value for 5ppm is 19.1, and the response value is about 23Under the OH detection condition, the best response value is obtained at 5ppm, and meanwhile, certain research potential is proved under the condition of lower concentration methanol.
The gas-sensitive material with the bow-tie type nano particles in the shape structure is prepared by combining a simple hydrothermal method, has a large specific surface area, improves the electron mobility, is simple, convenient and safe in preparation method, low in cost and high in practicability, and fills up the defect of detecting CH under a low-concentration condition3Blank OH gas response. The gas-sensitive material prepared by the invention has the sensitivity of 19 to 5ppm of methanol gas at the optimal working temperature of 200 ℃ under the conditions of lower working temperature and relative humidity of 0-80%, has specific sensing characteristics to the methanol gas, and can realize effective detection of the methanol at low temperature. The invention can be used for detecting the concentration of methanol, and is particularly suitable for being used as a preferred new material for detecting the methanol which is the marker gas of early respiratory gas of lung cancer.
Comparative example 1
(1) At normal temperature, 4.05g of Co (NO) is added3)2·6H2O, 4.5g of CO (NH)2)20.06g of NH4F, mixing with a proper amount of deionized water, and magnetically stirring to obtain 40ml of uniform mixed solution;
(2) transferring the obtained mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, reacting for 9 hours at 130 ℃, naturally cooling to room temperature after the reaction is finished, centrifuging, washing, and drying the product for 2 hours at 110 ℃ to obtain a precursor material;
(3) carrying out heat treatment on the obtained material precursor in air, wherein the heat treatment temperature is 350 ℃, keeping the temperature for 2h, the heating rate is 5 ℃/min, and then naturally cooling to room temperature to obtain Co3O4A bow-tie nanoparticle cluster material;
(4) adding deionized water into the obtained material, grinding to form paste, then uniformly coating the paste on the surface of the gas sensor, completely covering the platinum electrode, and drying at room temperature for 12h to form the gas-sensitive coating. Preheating the gas sensor with the dry coating in air at 300 ℃ for 24 hours to obtain Co3O4A bow-tie nanoparticle gas sensor;
(5) the flow meter is adjusted to feed in 0.5ppm, 1ppm and 5ppm of CH3OH, test Co3O4The collar-type nanoparticle gas sensor has a response value to a lower concentration.
The test shows that the response value for 0.5ppm is about 1.23, the response value for 1ppm is about 2.51, and the response value for 5ppm is 10.33, and CH is in the same concentration3The test data under the OH test conditions were inferior to the response values measured under the conditions of example 1.
Comparative example 2
(1) At normal temperature, 4.05 of Co (NO)3)2·6H2O, 4.25g of CO (NH)2)20.058g of NH4F, mixing with a proper amount of deionized water, and magnetically stirring to obtain 40ml of uniform mixed solution;
(2) transferring the obtained mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, reacting for 9 hours at 130 ℃, naturally cooling to room temperature after the reaction is finished, centrifuging, washing, and drying the product for 2 hours at 110 ℃ to obtain a precursor material;
(3) carrying out heat treatment on the obtained material precursor in air, wherein the heat treatment temperature is 350 ℃, keeping the temperature for 2h, the heating rate is 5 ℃/min, and then naturally cooling to room temperature to obtain Co3O4A bow-tie nanoparticle cluster material;
(4) adding deionized water into the obtained material, grinding to form paste, then uniformly coating the paste on the surface of the gas sensor, completely covering the platinum electrode, and drying at room temperature for 12h to form the gas-sensitive coating. Preheating the gas sensor with the dry coating in air at 300 ℃ for 24 hours to obtain Co3O4A bow-tie nanoparticle gas sensor;
(5) the flow meter is adjusted to feed in 0.5ppm, 1ppm and 5ppm of CH3OH, test Co3O4The collar-type nanoparticle gas sensor has a response value to a lower concentration.
The test shows that the response value for 0.5ppm is about 1.25, the response value for 1ppm is about 2.73, and the response value for 5ppm is 9.59, and CH is in the same concentration3Under the OH test conditions, the test data is inferior to the response values measured under the conditions of example 1.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (9)
1. A gas sensitive material for lung cancer breath marker gas methanol is characterized in that: the nano-scale structure comprises a plurality of groups of nano-components which are crossed together, wherein each nano-component comprises a plurality of nano-rods which are stacked together or are closely connected together, the diameter of each nano-rod is 0.2-0.3 mu m, and the length of each nano-rod is 10-20 mu m.
2. Use of the gas-sensitive material for lung cancer-oriented respiratory marker gas methanol according to claim 1 in the preparation of a gas sensor for detecting low-concentration methanol.
3. The method for preparing the gas-sensitive material for lung cancer respiratory marker gas methanol according to claim 1 or 2, which comprises: comprises the following steps of (a) carrying out,
dissolving cobalt salt, urea and ammonium fluoride in deionized water, and magnetically stirring at room temperature to obtain a mixed solution;
transferring the mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, heating for reaction for a period of time, naturally cooling to room temperature after the reaction is finished, centrifuging, washing and drying to obtain a precursor material;
and (3) carrying out heat treatment on the precursor material in air, and then naturally cooling to room temperature to obtain the gas-sensitive material.
4. The method for preparing the gas-sensitive material for lung cancer respiratory marker gas methanol according to claim 3, wherein the method comprises the following steps: the cobalt salt includes but is not limited to Co (NO)3)2·6H2O。
5. The method for preparing the gas-sensitive material for lung cancer respiratory marker gas methanol according to claim 3 or 4, wherein the method comprises the following steps: the mixed solution contains 4.05g of Co (NO) per 40ml of the mixed solution3)2·6H2O, 4.05 g-4.5 g of CO (NH)2)2And 0.056g to 0.06g of NH4F, and the balance of deionized water.
6. The method for preparing the gas-sensitive material for lung cancer respiratory marker gas methanol according to claim 5, wherein the method comprises the following steps: the mixed solution contains 4.05g of Co (NO) per 40ml of the mixed solution3)2·6H2O, 4.05g of CO (NH)2)2And 0.056g of NH4F, and the balance of deionized water.
7. The method for preparing the gas-sensitive material for lung cancer respiratory marker gas methanol according to claim 3 or 4, wherein the method comprises the following steps: the reaction temperature is 130 ℃, and the reaction time is 9 h.
8. The method for preparing the gas-sensitive material for lung cancer respiratory marker gas methanol according to claim 3, wherein the method comprises the following steps: the temperature of the heat treatment was 350 ℃.
9. The method for preparing the gas-sensitive material for the lung cancer respiratory marker gas methanol according to claim 3, 4 or 8, wherein the method comprises the following steps:
adding a gas-sensitive material into deionized water, grinding to form paste, uniformly coating the paste on the surface of a gas sensor, completely covering a platinum electrode, and drying at room temperature for 12 hours to form a gas-sensitive coating;
and (3) preheating the gas sensor with the dry coating in air at the temperature of 300 ℃ for 24 hours.
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